Pour point depressants for industrial lubricants containing mixtures of fatty acid esters and vegetable oils

Abstract

This invention relates to a composition containing the combination of: (A) at least one vegetable or synthetic triglyceride, (B) esters from the transesterification of at least one animal or vegetable oil triglyceride, (C) a pour point depressant, and (D) a performance additive. The composition may optionally contain (E) other oils.

What is claimed is: 
     
       1. A composition, comprising; (A) at least one vegetable or synthetic triglyceride oil of the formula ##STR44##  wherein R 1 , R 2  and R 3  are aliphatic hydrocarbyl groups having at least 60 percent monounsaturated character and containing from about 6 to about 24 carbon atoms;   (B) esters from the transesterification of at least one animal or vegetable oil triglyceride of the formula ##STR45##  with an alcohol or phenol R 4  OH wherein R 1 , R 2  and R 3  are aliphatic groups containing from about 6 to about 24 carbon atoms and R 4  is an aliphatic group containing from 1 to about 10 carbon atoms or an aromatic or substituted aromatic group containing from 6 to about 50 carbon atoms;   (C) a pour point depressant;   (D) at least one performance additive selected from the group consisting of (1) at least one alkyl phenol of the formula ##STR46##  wherein R 11  is an alkyl group containing from 1 up to about 24 carbon atoms and a is an integer of from 1 up to 5;   (2) a benzotriazole of the formula ##STR47##  wherein R 12  is hydrogen or an alkyl group of 1 up to about 24 carbon atoms;   (3) a phosphatide of the formula ##STR48##  wherein R 13  and R 14  are aliphatic hydrocarbyl groups containing from 8 to about 24 carbon atoms, and G is selected from the group consisting of hydrogen; ##STR49## (4) a thiocarbamate of the formula ##STR50##  wherein R 15  is an alkyl group containing from 1 to about 24 carbon atoms, phenyl or alkyl phenyl wherein the alkyl group contains from 1 to about 18 carbon atoms, R 16  and R 17  are hydrogen or an alkyl group containing from 1 to about 6 carbon atoms, with the proviso that R 16  and R 17  are not both hydrogen;   (5) citric acid and derivatives of citric acid of the formula ##STR51##  wherein R 18 , R 19  and R 20  are independently hydrogen or aliphatic hydrocarbyl groups containing from 1 to about 12 carbon atoms, or an aromatic or substituted aromatic groups containing from 6 to about 50 carbon atoms with the proviso that at least one of R 17 , R 18  and R 19  is an aliphatic hydrocarbyl group;   (6) a coupled phosphorus-containing amide of the formula ##STR52##  wherein X 1 , X 2  and X 3  independently is oxygen or sulfur; wherein R 21  and R 22 , independently is a hydrocarbyl, a hydrocarbyl-based oxy, the hydrocarbyl portions of which contain 6 to about 22 carbon atoms, or a hydrocarbyl-based thio, having from 4 to about 34 carbon atoms;     wherein R 23 , R 24 , R 25  and R 26 , independently is hydrogen, or an alkyl having from 1 to about 22 carbon atoms, or an aromatic, an alkyl-substituted aromatic or an aromatic-substituted alkyl having from 6 to about 34 atoms;   wherein n is zero or 1;   wherein n' is 2 or 3   wherein R 27  is hydrogen; and when n' is 2, R 28  is selected from the group consisting of ##STR53##  wherein R is an alkyl moiety, in the form of alkylene or alkylidene containing from 1 to 12 carbon atoms and R' is an alkyl moiety, alkylene, alkylidene or carboxyl containing 1 to 60 carbon atoms and when n' is 3, R 27  is ##STR54## (7) a methylacrylate derivative formed by the reaction of equal molar amounts of a phosphorus acid of the formula ##STR55##  with methylacrylate wherein X 1  and X 2  are oxygen or sulfur and R 29  and R 30  are each independently a hydrocarbyl, a hydrocarbyl-based thio or preferably a hydrocarbyl-based oxy group wherein the hydrocarbyl portion contains from 1 to about 30 carbon atoms and remaining acidity is neutralized with 1 mole propylene oxide for each 20-25 moles of phosphorus acid; (8) a metal overbased composition;   (9) a carboxylic dispersant composition;   (10) a nitrogen-containing organic composition comprising (a) an acylated, nitrogen containing compound having a substituent of at least 10 aliphatic carbon atoms made by reacting a carboxylic acylating agent with at least one amino compound containing at least one --NH group, said acylating agent being linked to said amino compound through an imido, amido, amidine or acyloxy ammonium linkage; and   (b) at least one amino phenol of the general formula ##STR56##  wherein R 37  is a substantially saturated, hydrocarbon-based substituent of at least 10 aliphatic carbon atoms; a, b and c are each independently an integer of one up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsaturated valences of Ar; and Ar is an aromatic moiety having 0-3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo or combinations of two or more of said substituents;     (11) a zinc salt of the formula ##STR57##  wherein R 43  and R 44  are independently hydrocarbyl groups containing from about 3 to about 20 carbon atoms;   (12) a sulfurized composition wherein the sulfurized composition is a sulfurized olefin prepared by reacting an olefin with sulfur or sulfur halide complex;   (13) at least one viscosity index improver; and   (14) at least one aromatic amine of the formula ##STR58##  wherein R 51  is ##STR59##  and R 52  and R 53  are independently a hydrogen or an alkyl group containing from 1 up to about 24 carbon atoms; and optionally   (E) at least one oil selected from the group consisting of   (1) synthetic ester base oil comprising the reaction of a monocarboxylic acid of the formula   R.sup.54 COOH        or a dicarboxylic acid of the formula ##STR60##  with an alcohol of the formula   R.sup.56 (OH).sub.n        wherein R 54  is a hydrocarbyl group containing from about 4 to about 24 carbon atoms, R 55  is hydrogen or a hydrocarbyl group containing from about 4 to about 50 carbon atoms, R 56  is a hydrocarbyl group containing from 1 to about 24 carbon atoms, m is an integer of from 0 to about 6 and n is an integer of from 1 to about 6; (2) a mineral oil;   (3) a polyalphaolefin; and   (4) a vegetable oil.       
     
     
       2. The composition of claim 1 wherein the triglyceride for (A) or (B) is a vegetable oil triglyceride. 
     
     
       3. The composition of claim 2 wherein the vegetable oil triglyceride is an ester of at least one straight chain fatty acid and glycerol wherein the fatty acid contains from about 8 to about 22 carbon atoms. 
     
     
       4. The composition of claim 3 wherein the triglyceride is at least 70 percent monounsaturated. 
     
     
       5. The composition of claim 4 wherein the triglyceride is at least 80 percent monounsaturated. 
     
     
       6. The composition of claim 5 wherein the monounsaturated character is due to an oleic acid residue. 
     
     
       7. The composition of claim 2 wherein the vegetable oil triglyceride comprises sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, meadowfoam oil or genetically modified sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil or meadowfoam oil. 
     
     
       8. The composition of claim 1 whereto R 4  contains from about 1 to about 6 carbon atoms. 
     
     
       9. The composition of claim 1 wherein the transesterification of (B) is carried out in the presence of a catalyst comprising alkali or alkaline earth metal alkoxides. 
     
     
       10. The composition of claim 1 wherein the transesterification is carried out at a temperature of ambient up to the decomposition temperature of any reactant or product. 
     
     
       11. The composition of claim 1 wherein the pour point depressant is a mixed ester characterized by low-temperature modifying properties of an ester of a carboxy-containing interpolymer, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2 and being derived from at least two monomers, one of said monomers being a low molecular weight aliphatic olefin, styrene or a substituted styrene wherein the substituent is a hydrocarbyl group containing from 1 up to about 18 carbon atoms, and the other of said monomers being an alpha, beta-unsaturated aliphatic acid, anhydride or ester thereof, said ester being substantially free of titratable acidity and being characterized by the presence within its polymeric structure of at least one of each of three pendant polar groups which are derived from the carboxy groups of said ester: (A) a relatively high molecular weight carboxylic ester group, said carboxylic ester group having at least 8 aliphatic carbon atoms in the ester radical,   (B) a relatively low molecular weight carboxylic ester group having no more than 7 aliphatic carbon atoms in the ester radical, wherein the molar ratio of (A):(B) of the pour point depressant is (1-20):1, and optionally   (C) a carbonyl-amino group derived from an amino compound having one primary or secondary amino group, wherein the molar ratio of (A):(B):(C) of the pour point depressant is (50-100):(5-50):(0.1-15).   
     
     
       12. The composition of claim 11 wherein said mixed ester of the interpolymer is characterized by low-temperature modifying properties of an ester of a carboxy-containing interpolymer, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2 and being derived from at least two monomers, the one being ethylene, propylene, isobutene, styrene or substituted styrene wherein the substituent is a hydrocarbyl group containing from 1 up to about 18 carbon atoms and the other of said monomers being maleic acid or anhydride, itaconic acid or anhydride or acrylic acid or ester, said ester being substantially free of titratable acidity and being characterized by the presence within its polymeric structure of at least one of each of three pendant polar groups which are derived from the carboxy groups of said ester: (A) a relatively high molecular weight carboxylic ester group, said carboxylic ester group having at least 8 aliphatic carbon atoms in the ester radical,   (B) a relatively low molecular weight carboxylic ester group having no more than 7 aliphatic carbon atoms in the ester radical, wherein the molar ratio of (A):(B) of the pour point depressant is (1-20):1, and optionally   (C) a carbonyl-amino group derived from an amino compound having one primary or secondary amino radical, wherein the molar ratio of (A):(B):(C) of the pour point depressant is (50-100):(5-50):(0.1-15).   
     
     
       13. The composition of claim 11 wherein the molar ratio of (A):(B) of the pour point depressant is ( 1-10):1. 
     
     
       14. The composition of claim 11 wherein the molar ratio of (A):(B):(C) of the pour point depressant is (70-85):(15-30):(3-4). 
     
     
       15. The composition of claim 11 wherein the interpolymer is a styrene-maleic anhydride interpolymer having a reduced specific viscosity of from about 0.1 to about 1. 
     
     
       16. The composition of claim 11 wherein the relatively high molecular weight carboxylic ester group of (A) has from 8 to 24 aliphatic carbon atoms, the relatively low molecular weight carboxylic ester group of (B) has from 3 to 5 carbon atoms and the carbonyl-amino group of (C) is derived from a primary-aminoalkyl-substituted tertiary amine. 
     
     
       17. The composition of claim 11 wherein the carboxy-containing interpolymer is a terpolymer of one molar proportion of styrene, one molar proportion of maleic anhydride, and less than about 0.3 molar proportion of a vinyl monomer. 
     
     
       18. The composition of claim 11 wherein said low molecular weight aliphatic olefin of said nitrogen-containing ester is selected from the group consisting of ethylene, propylene or isobutene. 
     
     
       19. The composition of claim 1 wherein the pour point depressant is an acrylate polymer of the formula ##STR61## wherein R 5  is hydrogen or a lower alkyl group containing from 1 to about 4 carbon atoms, R 6  is a mixture of alkyl, cycloalkyl or aromatic groups containing from about 4 to about 24 carbon atoms, and x is an integer providing a weight average molecular weight (Mw) to the acrylate polymer of about 5000 to about 1,000,000. 
     
     
       20. The composition of claim 19 wherein R 5  is a methyl group. 
     
     
       21. The composition of claim 19 wherein the molecular weight of the polymer is from about 50,000 to about 500,000. 
     
     
       22. The composition of claim 1 wherein the pour point depressant is a mixture of compounds having the general structural formula   Ar(R.sup.7)--[Ar'(R.sup.8)].sub.n --Ar"     wherein the Ar, Ar' and Ar" are independently an aromatic moiety containing 1 to 3 aromatic rings and the mixture includes compounds wherein moieties are present with 0 substituents, 1 substituent, 2 substituents and 3 substituents, R 7  and R 8  are independently an alkylene containing about 1 to 100 carbon atoms, and n is 0 to 1000.   
     
     
       23. The mixture as claimed in claim 22, wherein compounds are present in the mixture wherein the aromatic moieties are naphthalene, the olefin contains about 16 to 18 carbon atoms and the chlorinated hydrocarbon contains about 20 to 26 carbon atoms. 
     
     
       24. The mixture as claimed in claim 22 including compounds having a molecular weight ranging from about 300 to about 10,000. 
     
     
       25. The mixture as claimed in claim 22 including compounds having a molecular weight ranging from about 300 to about 300,000. 
     
     
       26. The composition of claim 1 wherein the pour point depressant is a nitrogen containing polymer prepared by polymerizing an acrylate ester monomer of the formula ##STR62## wherein R 9  is hydrogen or an alkyl group containing from 1 to about 4 carbon atoms and R 10  is an alkyl, cycloalkyl or aromatic group containing from 4 to about 24 carbon atoms with a nitrogen-containing monomer at from 0.001-1.0 moles of the nitrogen containing monomer for each mole of the acrylate ester monomer. 
     
     
       27. The composition of claim 26 wherein the nitrogen-containing monomer is selected from the group consisting of 4-vinylpyridine, 2-vinylpyridine, 2-N-morpholinoethyl methacrylate, N ,N-dimethylaminoethyl methacrylate and N,N-dimethylaminopropyl methacrylate. 
     
     
       28. The composition of claim 1 wherein within (D)(1) a is 2 and R 11  contains from 1 up to about 8 carbon atoms. 
     
     
       29. The composition of claim 28 wherein the alkyl phenol is of the formula ##STR63## wherein R 11  is t-butyl. 
     
     
       30. The composition of claim 1 wherein within (D)(2) R 12  is hydrogen or an alkyl group containing from 1 up to about 8 carbon atoms. 
     
     
       31. The composition of claim 1 wherein within (D)(2) R 12  is a methyl group. 
     
     
       32. The composition of claim 1 wherein within (D)(7) X 1  and X 2  are sulfur and R 29  and R 30  are hydrocarbyl-based oxy groups wherein the hydrocarbyl group contains from 1 to 12 carbon atoms. 
     
     
       33. The composition of claim 1 wherein within (D)(8) the metal overbased composition is selected from the group consisting of (a) a metal overbased phenate derived from the reaction of an alkylated phenol wherein the alkyl group has at least 6 aliphatic carbon atoms optionally reacted with formaldehyde or a sulfurization agent or mixtures thereof,   (b) a metal overbased sulfonate derived from an alkylated aryl sulfonic acid wherein the alkyl group has at least 15 aliphatic carbon atoms and   (c) a metal overbased carboxylate derived from fatty acids having at least 8 aliphatic carbon atoms.   
     
     
       34. The composition of claim 33 wherein the metal is an alkali or alkaline earth metal. 
     
     
       35. The composition of claim 33 wherein the alkaline earth metal is calcium or magnesium. 
     
     
       36. The composition of claim 33 wherein the alkali metal is sodium. 
     
     
       37. The composition of claim 33 wherein the metal overbased composition is treated with a borating agent. 
     
     
       38. The composition of claim 1 wherein within (D)(9) the carboxylic dispersant composition comprises the reaction of a hydrocarbon substituted succinic acid-producing compound with at least about one-half equivalent, per equivalent of acid producing compound, of an organic hydroxy compound or an amine containing at least one hydrogen attached to a nitrogen atom, or a mixture of said hydroxy compound and amine. 
     
     
       39. The composition of claim 38 wherein within (D)(9) the succinic acid-producing compound contains an average of at least about 50 aliphatic carbon atoms in the substituent. 
     
     
       40. The composition of claim 38 wherein within (D)(9) the succinic acid producing compound is selected from the group consisting of succinic acids, anhydrides, esters and halides. 
     
     
       41. The composition of claim 38 wherein within (D)(9) the hydrocarbon substituent of the succinic acid producing compound is derived from a polyolefin having an Mn value within the range of from about 700 to about 10,000. 
     
     
       42. The composition of claim 38 wherein within (D)(9) the amine reacted with the succinic acid producing compound is characterized by the formula   R.sup.35 R.sup.36 NH     wherein R 35  and R 36  are each independently hydrogen, or hydrocarbon, amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, and acylimidoyl groups provided that only one of R 35  and R 36  may be hydrogen.   
     
     
       43. The composition of claim 38 wherein within (D)(9) the amine reacted with the succinic acid producing compound is a polyamine. 
     
     
       44. The composition of claim 1 wherein within (D)(10)(a) the amino compound is an alkylene polyamine of the general formula ##STR64## wherein U is an alkylene group of 2 to 10 carbon atoms; each R 38  is independently a hydrogen atom, a lower alkyl group or a lower hydroxy alkyl group, with the proviso that at least one R 8  is a hydrogen atom, and n is 1 to 10. 
     
     
       45. The composition of claim 44 wherein within (D)(10)(a) the acylating agent is a mono- or polycarboxylic acid, or reactant equivalent thereof, containing an aliphatic hydrocarbyl substituent of at least about 30 carbon atoms. 
     
     
       46. The composition of claim 45 wherein within (D)(10)(a) the substituent is made from a homo- or interpolymer of a C 2-10  1-monoolefin or mixtures thereof. 
     
     
       47. The composition of claim 46 wherein within (D)(10)(a) the homo- or interpolymer is of ethylene, propylene, 1-butene, 2-butene, isobutene or mixtures thereof. 
     
     
       48. The composition of claim 44 wherein within (D)(10)(a) the acylating agent is at least one mono-carboxylic acid, or reactant equivalent thereof, having from 12 to 30 carbon atoms. 
     
     
       49. The composition of claim 48 wherein within (D)(10)(a) the acylating agent is a mixture of fatty monocarboxylic acids, or reactant equivalent thereof, having straight and branched carbon chains. 
     
     
       50. The composition of claim 49 wherein within (D)(10)(a) the amino compound is an ethylene, propylene or trimethylene polyamine of at least 2 to about 8 amino groups or mixtures of such polyamines. 
     
     
       51. The composition of claim 1 wherein within (D)(10)(b) R 37  contains up to about 750 carbon atoms and there are no optional substituents attached to Ar. 
     
     
       52. The composition of claim 51 wherein within (D)(10)(b) R 37  is an alkyl or alkenyl group. 
     
     
       53. The composition of claim 1 wherein within (D)(10)(b) R 37  contains about 30 to about 750 aliphatic carbon atoms and is made from a homo- or interpolymer of C 2  -C 10  olefins. 
     
     
       54. The composition of claim 53 wherein within (D)(10)(b) said olefins are selected from the group consisting of ethylene, propylene, butylene and mixtures thereof. 
     
     
       55. The composition of claim 1 wherein within (D)(10)(b) a, b and c are each 1, there are zero optional substituents attached to Ar, and Ar is a benzene nucleus. 
     
     
       56. The composition of claim 55 wherein within (D)(10)(b) R 37  is an alkyl or alkenyl group of at least about 30 carbon atoms and up to about 750 carbon atoms and is derived from a homo or interpolymer of C 2  -C 10  1-monoolefins. 
     
     
       57. The composition of claim 1 wherein within (D)(10)(b)the amino phenol is of the formula ##STR65## wherein R 39  is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic carbon atoms, R 40  is a member selected from the group consisting of lower alkyl, lower alkoxy, nitro, and halo; and z is zero or one. 
     
     
       58. The composition of claim 57 wherein within (D)(10)(b) R 39  is a purely hydrocarbyl aliphatic group of at least about 50 carbon atoms and is made from a polymer or interpolymer of an olefin selected from the group consisting of C 2-10  1-monoolefins and mixtures thereof. 
     
     
       59. The composition of claim 58 wherein within (D)(10)(b) z is zero. 
     
     
       60. The composition of claim 1 wherein within (D)(12) the olefin is an alkylene compound containing one double bond and 2 to 50 carbon atoms, and the sulfur halide is a sulfur chloride. 
     
     
       61. The composition of claim 1 wherein within (D)(12) the olefin is a mixture of olefins containing isobutene and the sulfur halide is selected from the group consisting of sulfur monochloride, sulfur dichloride and mixtures thereof; the protic solvent is selected from the group consisting of water, alcohols, carboxylic acids and combination thereof; and the metal ions are sodium sulfide/sodium hydrosulfide mixture derived from hydrocarbon purification process streams and sodium hydroxide. 
     
     
       62. The composition of claim 1 wherein within (D)(12) the sodium sulfide/sodium hydrosulfide mixture is derived from hydrocarbon purification process streams. 
     
     
       63. The composition of claim 1 wherein within (D)(12) the olefin contains one double bond and 2 to 50 carbon atoms and the sulfur halide is a sulfur chloride. 
     
     
       64. The composition of claim 63 wherein within (D)(12) the olefin is isobutene, the sulfur halide is sulfur monochloride, and the protic solvent is a water-isopropyl alcohol mixture. 
     
     
       65. The composition of claim 1 wherein within (D)(12) the molar ratio of sulfur to adduct is from about 2:1 to about 4:1. 
     
     
       66. The composition of claim 65 wherein within (D)(12) the diene is further characterized in that R 47  and R 48  are hydrogen and R 45 , R 46 , R 49  and R 50  are each independently hydrogen, chloro, or lower alkyl. 
     
     
       67. The composition of claim 62 wherein within (D)(12) the diene is 1,3-butadiene. 
     
     
       68. The composition of claim 1 wherein within (D)(14) R 51  is ##STR66## and R 52  and R 53  are alkyl groups containing from 4 to 18 carbon atoms. 
     
     
       69. The composition of claim 68 wherein within (D)(14) R 52  and R 53  are nonyl groups.